Techn. Hochsch., Diss., 2005--Aachen.

Lutetium oxide doped with europium (Lu2O3:Eu3+) has been established as a promising scintillator material with properties that are advantageous when compared to other scintillators such as cesium iodide doped with thallium (CsI:Tl). Due to high X-ray attenuation characteristics, Lu2O3:Eu3+ is an attractive material for use in high resolution digital X-ray imaging systems. However, challenges still remain especially in the area of light output for Lu2O3:Eu3+. Processing by physical vapor deposition (PVD) and manipulation of oxygen defect structure was explored in order to better understand the effect on the scintillation phenomena. PVD results were obtained using high temperature radio frequency sputtering (RF) and pulsed laser deposition (PLD) systems. Characterization of light output by radial noise power spectrum density measurements revealed that high temperature RF films were superior to those obtained using PLD. Optimization of sputtered films based on light output over a range of process parameters, namely temperature, power, pressure, and substrate orientation was investigated. Parameterization of deposition conditions revealed that: 75 watts, 10.00 mtorr, and 800°C were optimum conditions for Lu2O3:Eu3+ films. Manipulation of anionic defect structure in similar material systems has been shown to improve scintillation response. Similar methods for Lu2O3:Eu3+ were explored for hot pressed samples of Lu2O3:Eu3+; via controlled atmosphere annealing, and use of extrinsic co-doping with calcium. The controlled atmosphere experiments established the importance of oxygen defect structure within Lu2O3:Eu3+ and showed that fully oxidized samples were preferred for light output. The second method utilized co-doping by the addition of calcium which induced oxygen vacancies and by Frenkel equilibrium changed the oxygen interstitial population within the Lu2O3:Eu3+ structure. The addition of calcium was investigated and revealed that scintillation was improved with a maximum response occurring at 340ppm of calcium. PVD optimization and co-doping experimental results provided a template for the use of calcium co-doped Lu2O3:Eu3+ targets for deposition of films. Preliminary deposition results were promising and revealed that small additions (around 550 ppm) of calcium resulted in better activator efficiency. Calcium co-doped films have a predicted increase in the light yield greater than 14% when compared to analogous un-doped Lu2O3:Eu3+ films at 60keV.

Em um processo de fabricação de revestimentos cerâmicos por via úmida há vários custos relacionados à atomização - processo no qual ocorre à pulverização e secagem da suspensão cerâmica - tais como: combustível, manutenção e perda de produção. O principal custo da manutenção está relacionado com a troca do bico desgastado, em especial o componente interno (pastilha furada) de WC-Co, que tem vida útil de cinco dias, devido ao elevado desgaste erosivo provocado pelas partículas cerâmicas. Neste trabalho foi realizado tratamento superficial, o qual consiste na aplicação de filmes finos (AlCrN, AlCrN_TiSiN e TiAlN) sobre as pastilhas furadas de WC-Co via PAPVD (deposição física de vapor assistida por plasma) para aumentar sua resistência ao desgaste. Indentações Rockwell “A” com carga de 60 kgf foram realizadas para caracterizar a adesão dos filmes nos substratos. Em seguida as pastilhas furadas de WCCo com tratamento e sem tratamento foram caracterizadas quanto à rugosidade, fases presentes por difração de raios X, microdureza, e carga de ruptura e espessura dos revestimentos. Analisou-se a microestrutura transversal e superficial das amostras tratadas e não tratadas através do microscópio eletrônico de varredura (MEV). Também foi desenvolvido um pulverizador de bancada piloto para testes, no qual pastilhas furadas revestidas e não revestidas foram testadas usando-se uma suspensão cerâmica de feldspato. A pastilha revestida que obteve menor desgaste erosivo no protótipo foi a WC-Co + AlCrN. Este recobrimento apresentou propriedades intermediárias de dureza e boa qualidade de adesão em relação aos demais tratamentos empregados. Em seguida, substratos de dois fornecedores (“A” e “B”) foram revestidos com AlCrN para serem testados em um atomizador industrial. Nesta aplicação, os melhores resultados foram obtidos para os substratos do fornecedor “A”. Observou-se que as amostras do fornecedor “A” apresentaram dureza similar em relação às amostras do fornecedor “B”, porém, somente as amostras do fornecedor “A” foram aprovadas em relação à qualidade de adesão, conforme a norma alemã VDI 3198. Foi possível estimar um aumento de 40% na vida útil da pastilha furada. / In a spray-drying process of a ceramic suspension for production of ceramic tiles there are many costs related to: fuel, maintenance and productions losses. The main cost in maintenance is related to the exchange of the worn spray nozzle, especially the nozzle stuck, an internal component made of WC-Co that has a shelf life of five days due to the high erosive wear caused by ceramics particles. In this work surface treatment to produce thin films (AlCrN, AlCrN_TiSiN e TiAlN) on the nozzle stuck, made of WCCo, via PAPVD (Plasma Assisted Physical Vapor Deposition) was carried out in order to increase its wear resistance. Rockwell “A” indentation with 60 kgf loading was used in order to characterize the adhesion of films. The films and the substrate were also characterized by x-ray diffraction, roughness, microhardness, rupture load, and coating thickness. The microstructure was analyzed by SEM. A spray pilot bench was constructed for testing the parts with or without treatment using a ceramic suspension of feldspar. The samples who achieved less erosive wear in the prototype was WCCo+ AlCrN. This coating developed higher adhesion and intermediate hardness compared to other treatments. Substrates from two suppliers ("A" and "B") were treated with AlCrN and subsequently tested in an industrial spray-dyer. In this application the best results were obtained for the substrates of supplier "A". It was observed that samples of supplier "A" showed similar hardness for the samples from "B", but adherence was significantly greater for supplier "A". It could be estimate an increasing of 40% in a shelf life of a nozzle stuck.

Em um processo de fabricação de revestimentos cerâmicos por via úmida há vários custos relacionados à atomização - processo no qual ocorre à pulverização e secagem da suspensão cerâmica - tais como: combustível, manutenção e perda de produção. O principal custo da manutenção está relacionado com a troca do bico desgastado, em especial o componente interno (pastilha furada) de WC-Co, que tem vida útil de cinco dias, devido ao elevado desgaste erosivo provocado pelas partículas cerâmicas. Neste trabalho foi realizado tratamento superficial, o qual consiste na aplicação de filmes finos (AlCrN, AlCrN_TiSiN e TiAlN) sobre as pastilhas furadas de WC-Co via PAPVD (deposição física de vapor assistida por plasma) para aumentar sua resistência ao desgaste. Indentações Rockwell “A” com carga de 60 kgf foram realizadas para caracterizar a adesão dos filmes nos substratos. Em seguida as pastilhas furadas de WCCo com tratamento e sem tratamento foram caracterizadas quanto à rugosidade, fases presentes por difração de raios X, microdureza, e carga de ruptura e espessura dos revestimentos. Analisou-se a microestrutura transversal e superficial das amostras tratadas e não tratadas através do microscópio eletrônico de varredura (MEV). Também foi desenvolvido um pulverizador de bancada piloto para testes, no qual pastilhas furadas revestidas e não revestidas foram testadas usando-se uma suspensão cerâmica de feldspato. A pastilha revestida que obteve menor desgaste erosivo no protótipo foi a WC-Co + AlCrN. Este recobrimento apresentou propriedades intermediárias de dureza e boa qualidade de adesão em relação aos demais tratamentos empregados. Em seguida, substratos de dois fornecedores (“A” e “B”) foram revestidos com AlCrN para serem testados em um atomizador industrial. Nesta aplicação, os melhores resultados foram obtidos para os substratos do fornecedor “A”. Observou-se que as amostras do fornecedor “A” apresentaram dureza similar em relação às amostras do fornecedor “B”, porém, somente as amostras do fornecedor “A” foram aprovadas em relação à qualidade de adesão, conforme a norma alemã VDI 3198. Foi possível estimar um aumento de 40% na vida útil da pastilha furada. / In a spray-drying process of a ceramic suspension for production of ceramic tiles there are many costs related to: fuel, maintenance and productions losses. The main cost in maintenance is related to the exchange of the worn spray nozzle, especially the nozzle stuck, an internal component made of WC-Co that has a shelf life of five days due to the high erosive wear caused by ceramics particles. In this work surface treatment to produce thin films (AlCrN, AlCrN_TiSiN e TiAlN) on the nozzle stuck, made of WCCo, via PAPVD (Plasma Assisted Physical Vapor Deposition) was carried out in order to increase its wear resistance. Rockwell “A” indentation with 60 kgf loading was used in order to characterize the adhesion of films. The films and the substrate were also characterized by x-ray diffraction, roughness, microhardness, rupture load, and coating thickness. The microstructure was analyzed by SEM. A spray pilot bench was constructed for testing the parts with or without treatment using a ceramic suspension of feldspar. The samples who achieved less erosive wear in the prototype was WCCo+ AlCrN. This coating developed higher adhesion and intermediate hardness compared to other treatments. Substrates from two suppliers ("A" and "B") were treated with AlCrN and subsequently tested in an industrial spray-dyer. In this application the best results were obtained for the substrates of supplier "A". It was observed that samples of supplier "A" showed similar hardness for the samples from "B", but adherence was significantly greater for supplier "A". It could be estimate an increasing of 40% in a shelf life of a nozzle stuck.

Tese (doutorado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Mecânica, 2015. / Submitted by Fernanda Percia França (fernandafranca@bce.unb.br) on 2015-11-20T19:59:26Z No. of bitstreams: 1 2015_EdgarSobralAshiuchi.pdf: 4822357 bytes, checksum: 0a5b84f109f0c56b9d9bd06d784e6ea3 (MD5) / Approved for entry into archive by Raquel Viana(raquelviana@bce.unb.br) on 2016-05-12T19:28:40Z (GMT) No. of bitstreams: 1 2015_EdgarSobralAshiuchi.pdf: 4822357 bytes, checksum: 0a5b84f109f0c56b9d9bd06d784e6ea3 (MD5) / Made available in DSpace on 2016-05-12T19:28:40Z (GMT). No. of bitstreams: 1 2015_EdgarSobralAshiuchi.pdf: 4822357 bytes, checksum: 0a5b84f109f0c56b9d9bd06d784e6ea3 (MD5) / Este trabalho tem como principal objetivo investigar os efeitos do tratamento criogênico profundo quanto à microabrasão na liga de alumínio laminado AA 6101-T4 com e sem o revestimento de CrN depositado por PVD. O material tal como recebido foi utilizado como referência de desempenho em ensaios de resistência ao desgaste microabrasivo para amostras que receberam o tratamento criogênico, o revestimento de CrN ou as combinações de ambos. O material tratado criogenicamente apresentou aumento relativo na resistência ao desgaste da ordem de 35%. Com uma combinação específica do tratamento criogênico profundo e do revestimento de filme fino de CrN, a resistência ao desgaste obteve incremento da ordem de 81%. Esse resultado da combinação do tratamento criogênico e do revestimento de CrN foi substancialmente superior aos obtidos para os materiais que receberam apenas um deles. Levando em consideração os mecanismos de desgaste manifestados no sistema tribológico, a dureza não demonstrou acompanhar o acréscimo da resistência ao desgaste. Estruturas nanométricas tais como aglomerados ou zonas de Guinier-Preston (GP) exibiram maior concentração nas amostras tratadas criogenicamente. De acordo com este trabalho, apenas a presença de tais nanoestruturas pôde ser associada ao aumento da resistência ao desgaste com a aplicação do tratamento criogênico profundo. Esta tese explora esse tipo de beneficiamento além dos limites da sua habitual aplicação para o aço. _______________________________________________________________________________________________ ABSTRACT / This work aimed to investigate the effects of deep cryogenic treatment with respect to the abrasion in rolled aluminum alloy AA 6101-T4 with and without the CrN coating deposited by PVD. The material as received was used as a performance benchmark in microabrasive wear resistance test for samples receiving the cryogenic treatment, the CrN coatings or combinations of both. The cryogenically treated material presented relative increase in wear resistance of the order of 35%. With a specific combination of deep cryogenic treatment and the thin CrN film coating, the wear resistance was an increase of approximately 81%. This results from the combination of the cryogenic treatment and CrN coating was substantially higher than those obtained for the materials that received only one of them. Taking into account the wear mechanisms manifested in the tribological system, the hardness did not show follow the wear resistance increase. Nanoscale structures such as clusters or Guinier-Preston(GP) zones exhibited highest concentration in the samples treated cryogenically. According to this work, only the presence of such nanostructures could be associated with increased wear resistance for the material cryogenic treated. This thesis explores the deep cryogenic treatment beyond the limits of their usual application for steel.

abstract: Pyrite is a 0.95 eV bandgap semiconductor which is purported to have great potential in widespread, low–cost photovoltaic cells. A thorough material selection process was used in the design of a pyrite sequential vapor deposition chamber aimed at reducing and possibly eliminating contamination during thin film growth. The design process focused on identifying materials that do not produce volatile components when exposed to high temperatures and high sulfur pressures. Once the materials were identified and design was completed, the ultra–high vacuum growth system was constructed and tested. Pyrite thin films were deposited using the upgraded sequential vapor deposition chamber by varying the substrate temperature from 250°C to 420°C during deposition, keeping sulfur pressure constant at 1 Torr. Secondary Ion Mass Spectrometry (SIMS) results showed that all contaminants in the films were reduced in concentration by orders of magnitude from those grown with the previous system. Characterization techniques of Rutherford Back–scattering Spectrometry (RBS), X–Ray Diffraction (XRD), Raman Spectroscopy, Optical Profilometry and UV/Vis/Near–IR Spectroscopy were performed on the deposited thin films. The results indicate that stoichiometric ratio of S:Fe, structural–quality (epitaxy), optical roughness and percentage of pyrite in the deposited thin films improve with increase in deposition temperature. A Tauc plot of the optical measurements indicates that the pyrite thin films have a bandgap of 0.94 eV. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

Em um processo de fabricação de revestimentos cerâmicos por via úmida há vários custos relacionados à atomização - processo no qual ocorre à pulverização e secagem da suspensão cerâmica - tais como: combustível, manutenção e perda de produção. O principal custo da manutenção está relacionado com a troca do bico desgastado, em especial o componente interno (pastilha furada) de WC-Co, que tem vida útil de cinco dias, devido ao elevado desgaste erosivo provocado pelas partículas cerâmicas. Neste trabalho foi realizado tratamento superficial, o qual consiste na aplicação de filmes finos (AlCrN, AlCrN_TiSiN e TiAlN) sobre as pastilhas furadas de WC-Co via PAPVD (deposição física de vapor assistida por plasma) para aumentar sua resistência ao desgaste. Indentações Rockwell “A” com carga de 60 kgf foram realizadas para caracterizar a adesão dos filmes nos substratos. Em seguida as pastilhas furadas de WCCo com tratamento e sem tratamento foram caracterizadas quanto à rugosidade, fases presentes por difração de raios X, microdureza, e carga de ruptura e espessura dos revestimentos. Analisou-se a microestrutura transversal e superficial das amostras tratadas e não tratadas através do microscópio eletrônico de varredura (MEV). Também foi desenvolvido um pulverizador de bancada piloto para testes, no qual pastilhas furadas revestidas e não revestidas foram testadas usando-se uma suspensão cerâmica de feldspato. A pastilha revestida que obteve menor desgaste erosivo no protótipo foi a WC-Co + AlCrN. Este recobrimento apresentou propriedades intermediárias de dureza e boa qualidade de adesão em relação aos demais tratamentos empregados. Em seguida, substratos de dois fornecedores (“A” e “B”) foram revestidos com AlCrN para serem testados em um atomizador industrial. Nesta aplicação, os melhores resultados foram obtidos para os substratos do fornecedor “A”. Observou-se que as amostras do fornecedor “A” apresentaram dureza similar em relação às amostras do fornecedor “B”, porém, somente as amostras do fornecedor “A” foram aprovadas em relação à qualidade de adesão, conforme a norma alemã VDI 3198. Foi possível estimar um aumento de 40% na vida útil da pastilha furada. / In a spray-drying process of a ceramic suspension for production of ceramic tiles there are many costs related to: fuel, maintenance and productions losses. The main cost in maintenance is related to the exchange of the worn spray nozzle, especially the nozzle stuck, an internal component made of WC-Co that has a shelf life of five days due to the high erosive wear caused by ceramics particles. In this work surface treatment to produce thin films (AlCrN, AlCrN_TiSiN e TiAlN) on the nozzle stuck, made of WCCo, via PAPVD (Plasma Assisted Physical Vapor Deposition) was carried out in order to increase its wear resistance. Rockwell “A” indentation with 60 kgf loading was used in order to characterize the adhesion of films. The films and the substrate were also characterized by x-ray diffraction, roughness, microhardness, rupture load, and coating thickness. The microstructure was analyzed by SEM. A spray pilot bench was constructed for testing the parts with or without treatment using a ceramic suspension of feldspar. The samples who achieved less erosive wear in the prototype was WCCo+ AlCrN. This coating developed higher adhesion and intermediate hardness compared to other treatments. Substrates from two suppliers ("A" and "B") were treated with AlCrN and subsequently tested in an industrial spray-dyer. In this application the best results were obtained for the substrates of supplier "A". It was observed that samples of supplier "A" showed similar hardness for the samples from "B", but adherence was significantly greater for supplier "A". It could be estimate an increasing of 40% in a shelf life of a nozzle stuck.

Hard nanostructured TiAlN coatings have gained high importance in the field of protective tribological coatings. Nevertheless, their use regarding high temperature (>800°C) applications such as dry high speed machining still remains a challenge. Addition of elements such as Ta or Y has shown a beneficial impact on these properties. But for a better performance of these coatings, an in-depth understanding of their oxidation and wear mechanisms over a wider range of temperatures is needed which is currently unavailable in the literature. This work investigated the wear and oxidation properties of AlTiTaN hard coatings deposited by reactive magnetron sputtering at a substrate temperature of 250°C. Depending on process conditions, coatings with a preferential crystallographic orientation of cubic {111} or {200} with a columnar microstructure were observed. The oxidation and wear mechanisms for these coatings were investigated between 700°C and 950°C in air for various test durations. Further, the influence of Y doping in AlTiTaN coating was also studied.By combining Dynamic-Secondary Ion Mass Spectrometry ,X-ray diffraction (XRD) and Transmission Electron Microscopy measurements, it was demonstrated that a single amorphous oxide layer comprising of Ti, Al and Ta oxides formed at 700°C became a bilayer composed of a crystalline Al rich layer (protective Al2O3) and a Ti/Ta rich oxide layer at 900°C. The oxidation mechanism was governed primarily by inward diffusion of O at 700°C while from 800°C onwards outward diffusion of Al and inward diffusion of O controlled the reaction rate. A correlation between the oxidation kinetics and wear mechanism of AlTiTaN coatings, investigated at 700°, 800° and 900°C, was established. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

The design of new engineering materials resistant to both wear damage and corrosion degradation becomes increasingly demanding in complex service conditions. Unfortunately, there is typically a tradeoff between wear and corrosion resistance, even for important passive metals such as Al alloys. This is because the presence of precipitates hardens the material but at the same time lead to unfavorable galvanic coupling between the precipitates and the matrix, resulting in accelerated corrosion. This work showed that Al (or Mg) supersaturated solid solution formed using non-equilibrium methods exhibited enhanced corrosion resistance without compromising strength. For Al, alloying with Mn up to ~ 20.at.% simultaneously increased the wear resistance of Al as well as the protectiveness of the passive layer, thus improving the overall tribocorrosion resistance. For Mg, alloying with Y (4.67 wt.%), Zr (0.45 wt%), and Nd (1.79 wt%) in solid solution led to ~ 8 fold increment in corrosion resistance in physiological environment. Magnetron-sputtered aluminum (Al) and aluminum–manganese (Al-Mn) films with structures ranging from nanocrystalline to amorphous were obtained by tuning the Mn% up to 20.5 at.%. Corrosion behavior of the films was investigated in 0.6 M and 0.01 M NaCl aqueous solutions by potentiodynamic polarization (PD) and electrochemical impedance spectroscopy (EIS). Pitting corrosion was found to be strongly affected by alloy composition. The amorphous Al–20.5 at.% Mn exhibited the best pitting resistance during short term exposure. However, over longer immersion in 0.01 M NaCl up to 108 hrs, nanocrystalline Al–5.2 at.% Mn showed the highest corrosion resistance. The dual-phase Al-11.5 at % Mn alloy was found to have higher nominal corrosion rate compared to its nanocrystalline or amorphous counterparts. The effects of Mn alloying on the tribocorrosion behavior of magnetron-sputtered Al-Mn thin films with 5.2 at.% and 20.5 at.% Mn were investigated in 0.6 M NaCl aqueous solution. Tribocorrosion resistance of Al-Mn was found to be strongly affected by the alloying composition and applied potential. Higher Mn content increased H/E ratio and promoted the formation of denser and more compact passive film, hence improving tribocorrosion resistance of Al. In particular, alloying with 20.5 at.% Mn led to an increase of the corrosion resistance by ~ 10 times and the hardness ~ 8 times compared to pure Al. The total material loss during tribocorrosion was found to increase with applied potential. When the applied potential was increased from cathodic to anodic, simultaneous contribution of the mechanical and the electrochemical wear leads to accelerated material loss. A galvanic cell model was used to investigate the depassivation-repassivation kinetics during tribocorrosion. It was found that alloying with 5.2 at.% Mn led to more than 10-fold reduction in the current density required to re-passivate similar worn areas compared to pure Al. The origin of wear-corrosion synergy was discussed based on these observations. Magnesium alloys such as WE43 are considered for biomedical applications including cardiovascular stents and bone implants due to their biocompatibility, good cell adhesion, and mechanical properties close to that of bones. Unfortunately, their high degradation rate and subsequent loss of structural integrity in physiological environments hinders such applications. To improve the corrosion resistance of WE43 magnesium alloy, its microstructure was optimized to prevent micro-galvanic coupling between Mg matrix and precipitates. Chemically homogeneous WE43 with nanoscale surface roughness was obtained by magnetron sputtering with high effective quench rate. The effect of chemical heterogeneity on the corrosion resistance of biodegradable WE43 magnesium alloy was studied by performing corrosion tests in blood bank buffered saline using samples from two metallurgical states, cast and deposited. The microstructure of all samples was investigated by grazing incidence X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The deposited samples, prepared by magnetron sputtering using targets with the same global composition as cast WE43, exhibited chemically homogeneous microstructure without the formation of secondary phases typically observed in the cast alloy. The corrosion behavior was studied by PD and EIS tests. It was found that the deposited alloy showed enhanced corrosion resistance, ~8-fold reduction in corrosion rate compared to the cast alloy, owing to the elimination of micro-galvanic coupling between the Mg matrix and the precipitates. In-situ monitoring of hydrogen bubble evolution during corrosion indicated significantly reduced cathodic reaction kinetics in the deposited alloy. Post-corrosion surface and cross-sectional SEM studies showed that the high corrosion rate in the cast alloy was associated with the formation of severely cracked corrosion products preferably around Zr- and Y-containing precipitates.

In this diploma thesis, literary research about drilling and coating technology focused on PVD coatings was performed. Furthermore, there is an overview of cutting materials. In the experimental part of the work, the attention is dedicated to tests of twist drills from cemented carbide and high-speed steel materials. For these drills, the feed force Ff and the cutting moment Mc were measured when drilling into austenitic stainless steel. At the end of this work, the technical and economic evaluation of the practical part is presented.